JP4422445B2 - Method of depositing a silicon dioxide layer on a substrate by atomic layer deposition - Google Patents
Method of depositing a silicon dioxide layer on a substrate by atomic layer deposition Download PDFInfo
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- JP4422445B2 JP4422445B2 JP2003271607A JP2003271607A JP4422445B2 JP 4422445 B2 JP4422445 B2 JP 4422445B2 JP 2003271607 A JP2003271607 A JP 2003271607A JP 2003271607 A JP2003271607 A JP 2003271607A JP 4422445 B2 JP4422445 B2 JP 4422445B2
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- 238000000034 method Methods 0.000 title claims description 183
- 239000000758 substrate Substances 0.000 title claims description 84
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims description 76
- 238000000231 atomic layer deposition Methods 0.000 title claims description 72
- 235000012239 silicon dioxide Nutrition 0.000 title claims description 38
- 239000000377 silicon dioxide Substances 0.000 title claims description 38
- 238000000151 deposition Methods 0.000 title claims description 22
- 239000000376 reactant Substances 0.000 claims description 118
- 239000003054 catalyst Substances 0.000 claims description 112
- 230000008569 process Effects 0.000 claims description 90
- 238000010926 purge Methods 0.000 claims description 45
- 239000010409 thin film Substances 0.000 claims description 44
- 238000006243 chemical reaction Methods 0.000 claims description 37
- 239000010410 layer Substances 0.000 claims description 36
- 239000011261 inert gas Substances 0.000 claims description 33
- 239000006227 byproduct Substances 0.000 claims description 28
- 229910052710 silicon Inorganic materials 0.000 claims description 23
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 22
- 230000008021 deposition Effects 0.000 claims description 20
- 239000004065 semiconductor Substances 0.000 claims description 19
- -1 tertiary aliphatic amine compound Chemical class 0.000 claims description 18
- 239000010703 silicon Substances 0.000 claims description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 14
- 150000001412 amines Chemical class 0.000 claims description 12
- 239000002356 single layer Substances 0.000 claims description 12
- 150000003510 tertiary aliphatic amines Chemical group 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 10
- 239000010408 film Substances 0.000 claims description 10
- 229910021529 ammonia Inorganic materials 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 150000003377 silicon compounds Chemical class 0.000 claims description 8
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 125000005843 halogen group Chemical group 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 238000000137 annealing Methods 0.000 claims description 3
- 239000000047 product Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000009832 plasma treatment Methods 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 37
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 18
- 229910003902 SiCl 4 Inorganic materials 0.000 description 16
- 150000003839 salts Chemical class 0.000 description 12
- 239000002243 precursor Substances 0.000 description 10
- 125000000524 functional group Chemical group 0.000 description 9
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 9
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 238000013459 approach Methods 0.000 description 6
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 238000001723 curing Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 229910052736 halogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 238000005086 pumping Methods 0.000 description 4
- 125000006850 spacer group Chemical group 0.000 description 4
- 238000001039 wet etching Methods 0.000 description 4
- 239000002585 base Substances 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- UMVBXBACMIOFDO-UHFFFAOYSA-N [N].[Si] Chemical compound [N].[Si] UMVBXBACMIOFDO-UHFFFAOYSA-N 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000007809 chemical reaction catalyst Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000013386 optimize process Methods 0.000 description 2
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 2
- 229910021332 silicide Inorganic materials 0.000 description 2
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 2
- 238000006557 surface reaction Methods 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 239000005046 Chlorosilane Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 239000002879 Lewis base Substances 0.000 description 1
- 229910008045 Si-Si Inorganic materials 0.000 description 1
- 229910006411 Si—Si Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
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- 238000004458 analytical method Methods 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000005906 dihydroxylation reaction Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
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- 150000002500 ions Chemical group 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 150000007527 lewis bases Chemical group 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004518 low pressure chemical vapour deposition Methods 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000000682 scanning probe acoustic microscopy Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000000427 thin-film deposition Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
- C23C16/401—Oxides containing silicon
- C23C16/402—Silicon dioxide
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
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- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
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- H01L21/31612—Deposition of SiO2 on a silicon body
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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- H01L21/02164—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material being a silicon oxide, e.g. SiO2
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- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
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- H01L21/02205—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition
- H01L21/02208—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si
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Description
本発明は、原子層堆積法を用いて、半導体製造等において基板上に二酸化シリコン層を成長させる方法の改良に関するものである。本発明の方法は、例えば、ゲート酸化膜又は誘電層に適用される二酸化シリコン層の特性全体にわたって極めて精密な制御を容易にするものである。本発明の方法は、半導体製造における、ゲートスペーサ、ゲート酸化膜、シリサイドブロッキング層、ビットラインスペーサ、レベル間誘電層、エッチング停止層、それらに関連する最終製品又は中間製品を製造する際に特に有効である。 The present invention relates to an improved method for growing a silicon dioxide layer on a substrate in semiconductor manufacturing or the like using atomic layer deposition. The method of the present invention facilitates very precise control over the overall properties of a silicon dioxide layer applied to, for example, a gate oxide or dielectric layer. The method of the present invention is particularly effective in manufacturing gate spacers, gate oxides, silicide blocking layers, bit line spacers, interlevel dielectric layers, etch stop layers, and related end products or intermediate products in semiconductor manufacturing. It is.
半導体装置の製造において、化学的気相堆積法(CVD)、低圧CVD(CVD)、又は、プラズマCVD(PECVD)等の従来の手法によって基板表面上に二酸化シリコン層を形成することがよくある。これらの手法は、比較的低温で良好なステップカバレージを提供すると認識されている。しかしながら、半導体装置の密度を増大すると、装置を構成する各要素の高さが高くなる。結果として、増大するパターン密度変動と対応する均一性の減少とに起因して問題が発生する。 In the manufacture of semiconductor devices, a silicon dioxide layer is often formed on the substrate surface by conventional techniques such as chemical vapor deposition (CVD), low pressure CVD (CVD), or plasma enhanced CVD (PECVD). These approaches are recognized to provide good step coverage at relatively low temperatures. However, when the density of the semiconductor device is increased, the height of each element constituting the device is increased. As a result, problems arise due to increasing pattern density variations and corresponding decrease in uniformity.
本願に参考文献として組み込まれている米国特許第6,090,442号明細書(以下、「クラウス’442」と称する)に教示されているように、これらの認識されている問題に対する一のアプローチは原子層堆積(ALD)技術である。しかしながら、クラウス’442は、ALD技術の大きな欠点は、表面反応が完了するためには、それらが通常600Kより高い温度と、109L(ここで、1L=10−6Torr sec)より大きな反応物質の照射とを必要とすると教示している。このような高温及び高照射処理は、このような処理の実施の困難性を含む種々の理由のために超薄膜の堆積に対して望ましくはない。 One approach to these recognized problems, as taught in US Pat. No. 6,090,442 (hereinafter referred to as “Klaus' 442”), incorporated herein by reference. Is an atomic layer deposition (ALD) technique. However, Klaus' 442 is a major drawback of ALD technology in that for surface reactions to be completed, they are typically temperatures above 600K and reactions greater than 10 9 L (where 1 L = 10 −6 Torr sec). Teaches that irradiation of the substance is required. Such high temperature and high irradiation processes are undesirable for ultra thin film deposition for a variety of reasons including the difficulty of performing such processes.
クラウス’442ではこのような問題に対する改良アプローチが教示している。クラウス’442では、触媒型二元反応シーケンス化学(catalyzed binary reaction sequence chemistry)を用いて室温で機能化基板上に原子層薄膜を成長される方法を提供している。さらに詳細には、クラウス’442特許によって、室温で実施する2元触媒促進型“半反応”を利用して、2段階原子層堆積(ALD)をOH終端基板上に二酸化シリコン膜を成長させるのに用いることができる。 Claus' 442 teaches an improved approach to this problem. Klaus' 442 provides a method for growing atomic layer thin films on functionalized substrates at room temperature using catalytic binary reaction sequence chemistry. More specifically, according to the Claus' 442 patent, a two-step atomic layer deposition (ALD) is grown on an OH-terminated substrate using a two-catalyst-promoted “half-reaction” performed at room temperature. Can be used.
特定の実施形態では、クラウス’442は“第1の分子前駆体”としてSiCl4を、触媒としてピリジンを用いる。第1に、基板を、例えば、H2Oを用いて“第1の官能基”としてOH−で機能化する。次に、機能化基板を、ルイス塩基又はルイス酸(例えば、ピリジン)である触媒と、成長させる膜の主要要素及び第2の官能基(例えば、SiCl4)を含む第1の分子前駆体とに曝す。クラウス’442に示されているように、第1の“半反応”において、触媒は機能化基板の第1の官能基と反応し;次いで、第1の分子前駆体は(触媒によって活性化された)第1の官能基と反応して、触媒の置換と、基板の第1の官能基と第1の分子前駆体の主要要素との間の結合とを生ずる。合わせると、これらの2つの反応は第1の“半反応”を備え、膜の表面にわたって配置するようになった第2の官能基と膜形成を始める。 In certain embodiments, Claus' 442 uses SiCl 4 as the “first molecular precursor” and pyridine as the catalyst. First, the substrate is functionalized with OH − as the “first functional group” using, for example, H 2 O. Next, the functionalized substrate comprises a catalyst that is a Lewis base or a Lewis acid (eg, pyridine) and a first molecular precursor that includes a major element of the film to be grown and a second functional group (eg, SiCl 4 ). Expose to. As shown in Claus' 442, in the first “half-reaction”, the catalyst reacts with the first functional group of the functionalized substrate; the first molecular precursor is then (activated by the catalyst). Reacting with the first functional group results in displacement of the catalyst and bonding between the first functional group of the substrate and the main element of the first molecular precursor. Together, these two reactions comprise a first “semi-reaction” and begin film formation with a second functional group that is designed to be placed across the surface of the film.
クラウス’442プロセスにおいてこの点では、過剰な第1の分子前駆体と副産物とが反応チャンバから除去され、部分的に反応した基板を付加した触媒と第2の分子前駆体とに曝される。触媒は、反応することによって膜の表面に沿って曝された第2の官能基を活性化し、第2の分子前駆体と共に、第2の官能基の置換と、第1の分子前駆体の主要要素への結合とを生ずる。第2の分子前駆体は、第1の分子前駆体の主要要素と触媒との間の結合と反応して、触媒の置換と新しく成長した表面層上への第1の官能基の堆積とを生じ、それによって、フル成長/堆積サイクルが完了し、次のサイクルの準備において基板表面を機能化状態に戻す。 At this point in the Claus' 442 process, excess first molecular precursors and by-products are removed from the reaction chamber and exposed to a partially reacted substrate and a second molecular precursor. The catalyst reacts to activate the second functional group exposed along the surface of the membrane, along with the second molecular precursor, the substitution of the second functional group, and the main of the first molecular precursor. To the element. The second molecular precursor reacts with the bond between the primary component of the first molecular precursor and the catalyst to effect catalyst replacement and deposition of the first functional group on the newly grown surface layer. Occurs, thereby completing the full growth / deposition cycle and returning the substrate surface to a functionalized state in preparation for the next cycle.
クラウス’442特許の触媒補助堆積プロセスはALD技術の実質的な進歩を示すものであり、室温ALDを可能にするものではあるが、クラウス’442技術を用いて成長させた薄膜の表面密度、均一性及び品質は半導体産業において要求された標準には合致しないことがわかった。より小型のマイクロエレクトロニクスコンポーネントへの終わりなき進歩によって、半導体装置の特性にわたってより精密な制御が必要となる。このような精密な制御は、より均一な表面特性及びパターン密度を必要とする。本発明のALD技術の新たな進歩は、従来技術より優れた表面密度とより均一な表面特性とを有する半導体装置用の薄膜を生成し、その結果、薄膜層の特性全般にわたる顕著に精密な制御と、現在の小型化に適したより高品質な半導体装置の製造とが可能となる。 The catalyst-assisted deposition process of the Klaus '442 patent represents a substantial advance in ALD technology and allows room temperature ALD, but the surface density and uniformity of thin films grown using Klaus' 442 technology It has been found that the quality and quality do not meet the standards required in the semiconductor industry. Endless advances to smaller microelectronic components require more precise control over the characteristics of semiconductor devices. Such precise control requires more uniform surface properties and pattern density. The new advances in ALD technology of the present invention produce thin films for semiconductor devices that have better surface density and more uniform surface characteristics than the prior art, resulting in significantly more precise control over the overall characteristics of the thin film layer. This makes it possible to manufacture a higher quality semiconductor device suitable for the current miniaturization.
クラウス’442特許は、“トリエチルアミン((C2H5)3N)のような強いアミン塩基は、クロロシランの存在下で塩化トリエチルアンモニウム(NH+(C2H5)3Cl−)のような塩化合物を形成することを示した”旨記載している。この塩は表面を害し、この塩が成長するので反応効率を劣化する(カラム9、24〜28行)。従って、クラウス’442は、ALDの適用において、トリエチルアミン、すなわち第三脂肪族アミンの存在から離れる方向で教示している。 The Claus' 442 patent states that “a strong amine base such as triethylamine ((C 2 H 5 ) 3 N) is a salt such as triethylammonium chloride (NH + (C 2 H 5 ) 3 Cl—) in the presence of chlorosilane. "It has been shown to form a compound." This salt harms the surface, and this salt grows, degrading the reaction efficiency (column 9, lines 24 to 28). Thus, Claus' 442 teaches away from the presence of triethylamine, a tertiary aliphatic amine, in ALD applications.
従って、本発明の目的は、良好な表面密度、極めて高い純度を有し、表面特性を高精度で制御された非常に均一な薄膜を成長するために、原子層堆積法(ALD)を用いた方法を提供することである。 Accordingly, an object of the present invention is to use atomic layer deposition (ALD) to grow a very uniform thin film having good surface density, extremely high purity, and surface characteristics controlled with high precision. Is to provide a method.
本発明の他の目的は、反応物材料の一つとして少なくとも2つのシリコン原子を有するシリコン化合物を用いて半導体基板上に二酸化シリコン層を形成するALD法を提供することである。 Another object of the present invention is to provide an ALD method for forming a silicon dioxide layer on a semiconductor substrate using a silicon compound having at least two silicon atoms as one of the reactant materials.
本発明のさらに他の目的は、触媒材料として第三脂肪族アミン化合物を用いて半導体基板上に二酸化シリコン層を形成するALD法を提供することである。 Still another object of the present invention is to provide an ALD method for forming a silicon dioxide layer on a semiconductor substrate using a tertiary aliphatic amine compound as a catalyst material.
本発明のさらに他の目的は、本発明の方法を実施するために、最適の温度及び圧力範囲を提供することである。 Yet another object of the present invention is to provide optimal temperature and pressure ranges for carrying out the method of the present invention.
本発明のさらに他の目的は、本発明の方法の利益を増大するために、反応/パージプロセスシーケンス、タイミング及びこのような堆積サイクルを実施する技術を提供することである。 Yet another object of the present invention is to provide a reaction / purge process sequence, timing and techniques for performing such deposition cycles to increase the benefits of the method of the present invention.
本発明のさらに他の目的は、本発明の方法によって基板上に二酸化シリコン膜を硬化する方法を提供することである。 Yet another object of the present invention is to provide a method of curing a silicon dioxide film on a substrate by the method of the present invention.
本発明のさらに他の目的は、ゲートスペーサ、ゲート酸化膜、シリサイドブロッキング層、ビットラインスペーサ、レベル間誘電層、エッチング停止層等の用途において使用される基板の表面に沿って堆積された、優れた表面密度、極めて高い純度及び均一性を有する二酸化シリコン層を有する基板を備えた半導体装置を提供することである。 Yet another object of the present invention is the excellent deposition deposited along the surface of the substrate used in applications such as gate spacers, gate oxides, silicide blocking layers, bit line spacers, interlevel dielectric layers, etch stop layers, etc. And providing a semiconductor device comprising a substrate having a silicon dioxide layer having a high surface density, extremely high purity and uniformity.
本発明のさらに他の目的は、第1の反応物としてSi2Cl6を用いて、又は、触媒として第三脂肪族アミンを用いて、又は、その両方を用いて、半導体基板上に二酸化シリコン層を形成する触媒補助型ALD法を提供することである。 Yet another object of the present invention is to use silicon dioxide on a semiconductor substrate using Si 2 Cl 6 as the first reactant, or using a tertiary aliphatic amine as a catalyst, or both. It is to provide a catalyst assisted ALD method for forming a layer.
本発明のこれら及び他の目的や利点は、以下で議論するように、図面を参照して以下の詳細な説明によってよりよく理解されるだろう。 These and other objects and advantages of the present invention will be better understood by the following detailed description with reference to the drawings, as discussed below.
本発明は、半導体基板上に向上した特性及び純度を有する二酸化シリコン薄膜を形成するために触媒補助型原子層堆積法(ALD)を用いる改良された方法である。一の実施形態では、例えば、Si2Cl6のような少なくとも2個のシリコン原子を有するシリコン化合物をALDプロセスにおいて第1の反応物として用いる。第2の実施形態では、例えば、トリメチルアミンのような第三脂肪族アミン化合物をALDプロセスにおいて触媒として用いる。第3の実施形態では、ALDプロセスにおいて、少なくとも2個のシリコン原子を有するシリコン化合物を第1の反応物として用い、第三脂肪族アミン化合物を触媒として用いる。他の本発明の実施形態では、堆積した二酸化シリコン薄膜を硬化する方法を提供し、本発明の方法を実施する最適温度及び圧力条件を確立し、本発明の方法についての他の反応物/パージプロセスシーケンスについて記載する。 The present invention is an improved method of using catalytic assisted atomic layer deposition (ALD) to form silicon dioxide thin films having improved properties and purity on a semiconductor substrate. In one embodiment, a silicon compound having at least two silicon atoms such as, for example, Si 2 Cl 6 is used as the first reactant in the ALD process. In the second embodiment, for example, a tertiary aliphatic amine compound such as trimethylamine is used as a catalyst in the ALD process. In the third embodiment, in the ALD process, a silicon compound having at least two silicon atoms is used as a first reactant, and a tertiary aliphatic amine compound is used as a catalyst. Other embodiments of the present invention provide methods for curing deposited silicon dioxide thin films, establish optimal temperature and pressure conditions for performing the methods of the present invention, and other reactants / purges for the methods of the present invention. Describe the process sequence.
下の表1は、従来の高温ALD法、クラウス’442特許の触媒補助型ALD、及び本発明の3つの実施形態の理論的化学反応の比較をまとめたものである。
下の表2は、本発明の異なる実施形態に対応する触媒、第1の反応物、及び第2の反応物をまとめたものである。
図1は、触媒促進型の原子層堆積法(ALD)によって基板上に二酸化シリコン薄膜を形成する本発明の方法に一般的に適用される複数の段階、処理、連続的な化学反応を概略するフロー図である。 FIG. 1 outlines multiple steps, processes, and sequential chemical reactions that are typically applied to the method of the present invention for forming a silicon dioxide thin film on a substrate by catalyst-enhanced atomic layer deposition (ALD). FIG.
段階110
適当な機能化された基板を反応チャンバに入れる。
A suitable functionalized substrate is placed in the reaction chamber.
段階120
基板の温度が二酸化シリコンALDプロセスを開始するのに適した温度、典型的には約25℃−150℃に達するまで、基板を予備加熱する。
The substrate is preheated until the temperature of the substrate reaches a temperature suitable for initiating the silicon dioxide ALD process, typically about 25 ° C-150 ° C.
段階130
ALDによって、新しい二酸化シリコン層を基板表面に形成する。所望の厚さの二酸化シリコン薄膜が基板上に形成するまでサイクルを繰り返す。段階130は、以下に説明する小段階132−138から成る。
A new silicon dioxide layer is formed on the substrate surface by ALD. The cycle is repeated until a desired thickness of silicon dioxide thin film is formed on the substrate.
段階132
第1の反応物と触媒の混合物を反応チャンバに供給する。触媒は基板上で第1の反応物の反応活性化エネルギーを下げるように作用する。結果として、プロセス温度はほぼ室温まで又は室温よりわずかに高い温度まで低下する。
第1の反応物を供給すると、チャンバ内のプロセス温度は典型的には約25℃−150℃であり、好適には約90℃−110℃である。チャンバ内のプロセス圧力は典型的には約0.1〜100torrであり、好適には0.5〜5torrである。不活性ガス、例えば、アルゴン(Ar)を第1の反応物と触媒と共にチャンバに供給してもよい。
−OH反応サイトのHは、ハロゲン酸を形成するために、第1の塩基触媒の存在下で第1の反応物のハロゲン原子と反応する。ハロゲン酸は第1の塩基触媒を用いて中性化され、塩が生成される。同時に、第1の反応物のSi原子は、第1の生成物の化学吸着層を形成するために基板上の反応サイト上で酸素と反応する。
A mixture of the first reactant and catalyst is supplied to the reaction chamber. The catalyst acts to lower the reaction activation energy of the first reactant on the substrate. As a result, the process temperature decreases to approximately room temperature or slightly above room temperature.
Upon supplying the first reactant, the process temperature in the chamber is typically about 25 ° C.-150 ° C., preferably about 90 ° C.-110 ° C. The process pressure in the chamber is typically about 0.1-100 torr, preferably 0.5-5 torr. An inert gas, such as argon (Ar), may be supplied to the chamber along with the first reactant and the catalyst.
The -OH reaction site H reacts with the halogen atom of the first reactant in the presence of the first base catalyst to form a halogen acid. The halogen acid is neutralized using a first base catalyst to produce a salt. At the same time, the Si atoms of the first reactant react with oxygen on the reaction sites on the substrate to form a chemisorbed layer of the first product.
段落134
第1の反応プロセス(段落132)の副産物、例えば、塩、反応しなかった第1の反応物等を除去する。
Byproducts of the first reaction process (paragraph 132), such as salts, unreacted first reactants, etc. are removed.
段落136
(O及びHを含む)第2の反応物と第2の塩触媒の混合物をチャンバに供給し、第1の反応物の化学吸着層を第2の反応物と化学的に反応させる。
第2の反応物の例は、H2O、H2O2又はオゾンである。一の実施形態では、第2の塩触媒は第1の塩触媒と同じである。
第2の反応物を反応チャンバに供給するとき、チャンバ内の温度及び圧力の範囲は典型的には、段階132で使用された温度及び圧力の範囲とほぼ同じである。
この段階では、第2の反応物のO元素は、基板表面上に化学吸着したSiと反応する。第2の塩触媒の存在下で、第2の反応物のH元素はハロゲン原子と反応し、それによって、ハロゲン酸を生成する。次いで、このようなハロゲン酸と塩触媒との間の中和によって塩が生成する。
A mixture of a second reactant (including O and H) and a second salt catalyst is supplied to the chamber to chemically react the chemisorbed layer of the first reactant with the second reactant.
Examples of the second reactant are H 2 O, H 2 O 2 or ozone. In one embodiment, the second salt catalyst is the same as the first salt catalyst.
When supplying the second reactant to the reaction chamber, the temperature and pressure ranges in the chamber are typically about the same as the temperature and pressure ranges used in
At this stage, the O element of the second reactant reacts with Si chemisorbed on the substrate surface. In the presence of the second salt catalyst, the H element of the second reactant reacts with the halogen atom, thereby producing a halogen acid. The salt is then formed by neutralization between such a halogen acid and a salt catalyst.
段落138
第2の反応段階(段階136)の副産物を除去する。
The by-product of the second reaction stage (stage 136) is removed.
段落140
反応チャンバを排気して、チャンバ内に残留する堆積副産物を除去する。望ましくは、約90秒で段階を完了する。段階140の間、チャンバには気体は供給しない。
The reaction chamber is evacuated to remove deposition byproducts remaining in the chamber. Desirably, the stage is completed in about 90 seconds. During
段落150
その表面に沿ったSiO2薄膜の基板をチャンバから取り出す。
The substrate of the SiO 2 thin film along the surface is taken out from the chamber.
段落160
この段階は、新規に堆積したSiO2薄膜を硬化することを含む。本発明によって堆積した二酸化シリコン層を硬化するのに用いられる3つの方法がある。
1.熱処理:実質的な不活性ガス(すなわち、基板表面に対して不活性)例えば、窒素(N2)、酸素(O2)、水素(H2)、アルゴン(Ar)等の存在下で、約300℃−900℃で基板をアニールする。
2.プラズマ処理:酸素(O2)又は水素(H2)の存在下で、約200℃−700℃で基板をアニールする。
3.典型的には約25℃−700℃で、オゾン(O3)処理
This step involves curing the newly deposited SiO 2 film. There are three methods used to cure the silicon dioxide layer deposited according to the present invention.
1. Heat treatment: substantially inert gas (ie, inert to the substrate surface), for example, in the presence of nitrogen (N 2 ), oxygen (O 2 ), hydrogen (H 2 ), argon (Ar), etc. The substrate is annealed at 300 ° C-900 ° C.
2. Plasma treatment: annealing the substrate at about 200 ° C.-700 ° C. in the presence of oxygen (O 2 ) or hydrogen (H 2 ).
3. Typically ozone (O3) treatment at about 25 ° C-700 ° C
先述の3つの硬化法のいずれかを、本発明による触媒補助型ALDプロセスを用いて成長されたSiO2薄膜を使ってインサイチューで用いる。上の硬化方法2及び3が特に良好に働くことがわかった。
Any of the three curing methods described above are used in situ using SiO 2 thin films grown using the catalyst assisted ALD process according to the present invention. It has been found that the
第1の実施形態
本発明の第1の実施形態では、第1の反応物としてSi2Cl6又はそれと類似する化合物例えば、2個又は3個以上のシリコン原子を有するシリコンハライド(ハロゲン化物)を;第2の反応物として酸素と水素とを含む化合物例えば、H2O及び/又はH2O2を;触媒として塩化合物例えば、アンモニア又はアミンを;用いて水酸基を有する基板の機能化表面上に二酸化シリコン薄膜を生成する。本発明のこの実施形態では、第1の反応物は少なくとも2個のシリコン原子を有するシリコン化合物、例えば、Si2X6、Si3X8、Si4X10、及び以下の構造を有するSi3X6(三角形)から成る群から選択されたシリコンハライド化合物である。
図2で図示したように、第1の段階において、第1の反応物及び触媒の混合物を基板の水酸基機能化表面に曝すことによって、第1の反応物の化学吸着層を基板表面に沿って形成する。次いで、反応していない第1の反応物及び副産物を基板の領域から除去する。次のプロセス段階では、図2で図示したように、第1の反応物の化学吸着層は、触媒として塩化合物の存在下で第2の化合物と反応する。ここでその触媒は第1の反応物を反応する際に使用されるのと同じ触媒又は異なる塩化合物触媒であってもよい。この第2の反応段階の反応していない第2の反応物と副産物とを基板領域から除去する。新しくSiO2単層を含むようになった基板の表面は、新しいALDサイクルを始めるように準備された水酸基機能化状態に戻る。 As illustrated in FIG. 2, in the first stage, the chemical adsorbed layer of the first reactant along the substrate surface is exposed by exposing the mixture of the first reactant and catalyst to the hydroxyl functionalized surface of the substrate. Form. The unreacted first reactant and by-products are then removed from the area of the substrate. In the next process step, as illustrated in FIG. 2, the chemisorbed layer of the first reactant reacts with the second compound in the presence of a salt compound as a catalyst. Here, the catalyst may be the same catalyst used in reacting the first reactant or a different salt compound catalyst. The unreacted second reactant and by-products of this second reaction stage are removed from the substrate region. The surface of the substrate newly containing the SiO 2 monolayer returns to the hydroxyl functionalized state ready to begin a new ALD cycle.
前のプロセスはクラウス’442に記載された触媒補助型ALD技術によく似ているが、異なる反応物及び触媒の選択は、基板の薄膜表面層の性質及び品質において急激でかつ劇的なインパクトを呈することがわかった。一の重要な相異は、クラウス’442はSiCl4、すなわち、1個のシリコン原子を有するシリコンハライドの使用を教示する一方、本発明の上述の実施形態は、少なくとも2個のシリコン原子を有するシリコンハライド例えば、Si2Cl6を利用することである。この相異が成長率において大きな改善をもたらすことが本発明でわかった。特に、SiCl4単層は分子間に大きなスペースを有することがわかった。SiCl4の場合には、Si原子は基板上でO−Hサイトと反応し、Oと単結合を形成するときに、SiCl4は回転する。(反応に参加しない)Clの立体障害のために、次のO−Hサイトは他のSiCl4とは反応できない。他方、Si2Cl6単層は同時に2個のSi原子と反応でき、それによって、ALDプロセスの速度を向上する。さらに、その結果、表面に沿ってパッキングする分子がより密になり、二酸化シリコン層の品質が向上する。 The previous process is very similar to the catalyst-assisted ALD technique described in Claus' 442, but the selection of different reactants and catalysts has a dramatic and dramatic impact on the nature and quality of the thin film surface layer of the substrate. I found it to be present. One important difference is that Claus' 442 teaches the use of SiCl 4 , ie, a silicon halide having one silicon atom, while the above-described embodiments of the present invention have at least two silicon atoms. A silicon halide, for example, Si 2 Cl 6 is used. It has been found in the present invention that this difference provides a significant improvement in growth rate. In particular, it was found that the SiCl 4 monolayer has a large space between molecules. In the case of SiCl 4 , Si atoms react with O—H sites on the substrate, and SiCl 4 rotates when it forms a single bond with O. Due to the steric hindrance of Cl (which does not participate in the reaction), the next O—H site cannot react with other SiCl 4 . On the other hand, a Si 2 Cl 6 monolayer can react with two Si atoms simultaneously, thereby improving the speed of the ALD process. Furthermore, the result is a denser packing of molecules along the surface, improving the quality of the silicon dioxide layer.
以下に説明するように、図3−図6では、本発明のヘキサクロロシリコン(HCD)を用いて基板に成長したSiO2単層の特性及びパフォーマンスと、クラウス’442のテトラクロロシリコン(TCS)法を用いて成長したSiO2単層とを比較している。 As described below, in FIGS. 3-6, the characteristics and performance of a single layer of SiO 2 grown on a substrate using the hexachlorosilicon (HCD) of the present invention, and the tetrachlorosilicon (TCS) method of Claus' 442. And a SiO 2 single layer grown using
例えば、図3のグラフでは、種々のプロセス温度において、従来のSiCl4アプローチを用いた基板上へのSiO2単層の堆積速度と、本発明のSi2Cl6技術を利用して得られた堆積速度とを比較している。図3は、全てのプロセス温度で、Si2Cl6を用いた堆積速度(丸印)はSiCl4を用いた堆積速度(正方形印)のほぼ2倍である。 For example, the graph of FIG. 3 was obtained at various process temperatures using the deposition rate of a SiO 2 monolayer on a substrate using a conventional SiCl 4 approach and the Si 2 Cl 6 technique of the present invention. The deposition rate is compared. FIG. 3 shows that at all process temperatures, the deposition rate using Si 2 Cl 6 (circles) is approximately twice the deposition rate using SiCl 4 (squares).
図4は、従来のTCS(SiCl4)を用いて基板上に成長させた薄膜層の“シリコンリッチさ”と、本発明のHCD(Si2Cl6)を用いて基板上に成長させた薄膜の“シリコンリッチさ”とを比較している。種々のスパッタリング時間で、基板表面上のSiとOの原子濃度を測定するためにオージェ電子分光法を用いて、図4は、TCS技術を用いたOに対するSiの比は1:1.95であり、他方、HCD技術を用いたOに対するSiの比は1:1.84である。言い替えると、HCDアプローチを用いて形成した薄膜SiO2層はシリコンが“よりリッチ”であるのが望ましい。 FIG. 4 shows the “silicon richness” of a thin film layer grown on a substrate using conventional TCS (SiCl 4 ) and the thin film grown on the substrate using HCD (Si 2 Cl 6 ) of the present invention. The “silicon richness” of Using Auger electron spectroscopy to measure atomic concentrations of Si and O on the substrate surface at various sputtering times, FIG. 4 shows that the ratio of Si to O using the TCS technique is 1: 1.95. On the other hand, the ratio of Si to O using HCD technology is 1: 1.84. In other words, the thin film SiO 2 layer formed using the HCD approach is preferably “richer” in silicon.
図5Aは、HCD本発明のアプローチを用いて成長させたSiO2単層においてシリコンのシリコン結合状態と、従来のTCS法を用いて成長させた単層において結合状態とを比較するXPSデータを示す。図5Aのグラフに示された結合状態の差は、図4によって示されたシリコン“リッチさ”の差と共に、SiO2単層はTCS法の代わりにHCD法によって成長されたときに形成された異なるタイプのシリコン結合によって説明されていると思われる。図5Bに図示されているように、TCS法では、SiO2単層における隣接シリコン原子は中間の酸素原子だけを介して相互に結合すると考えられ、他方、本発明のHCD法では、SiO2単層において少なくとも複数の直接のSi−Si結合の生成につながると考えられる。 FIG. 5A shows XPS data comparing the silicon bonded state of silicon in a SiO 2 monolayer grown using the HCD inventive approach and the bonded state in a single layer grown using the conventional TCS method. . The bond state differences shown in the graph of FIG. 5A, together with the silicon “richness” differences shown by FIG. 4, were formed when the SiO 2 monolayer was grown by the HCD method instead of the TCS method. It seems to be explained by different types of silicon bonds. As shown in Figure 5B, the TCS method, considered adjacent silicon atoms in the SiO 2 single layer is bonded to each other only via the intermediate oxygen atom, and the other, with HCD method of the present invention, SiO 2 single It is believed that this leads to the formation of at least a plurality of direct Si-Si bonds in the layer.
図6は、本発明のHCD法を用いて形成されたSiO2薄膜に対するウェットエッチング速度と、従来のTCS法を用いて形成されたSiO2薄膜に対するウェットエッチング速度とを比較する(図6の棒グラフの縦スケールは両データを載せるために不連続になっている)。図6は、本発明のHCD法を用いて形成されたSiO2薄膜のウェットエッチング速度がTCS法を用いて形成されたSiO2薄膜より約6倍良好であることを示している。 FIG. 6 compares the wet etching rate for the SiO 2 thin film formed using the HCD method of the present invention with the wet etching rate for the SiO 2 thin film formed using the conventional TCS method (the bar graph of FIG. 6). The vertical scale is discontinuous to carry both data). FIG. 6 shows that the wet etching rate of the SiO 2 thin film formed using the HCD method of the present invention is about 6 times better than the SiO 2 thin film formed using the TCS method.
第2の実施形態
本発明の第2の実施形態では、第1の反応物としてシリコンハライドと;酸素及び水素原子を含む第2の反応物例えば、H2O及び/又はH2O2と;三元脂肪化合物アミン触媒と;用いて基板の機能化表面上に二酸化シリコン薄膜を生成する。本発明のこの実施形態では、第1のプロセス段階において基板の機能化表面を第1の反応物と触媒との混合物に曝すことによって、第1の反応物の化学吸着層を基板表面に沿って形成する。次いで、反応しなかった第1の反応物と副産物とを基板のその領域から除去する。次のプロセス段階において、第1の反応物の化学吸着層が三元脂肪化合物アミン触媒の存在下で第2の反応物と反応する。この第2のプロセス段階の副産物を基板領域から除去する。
Second Embodiment In the second embodiment of the present invention, a silicon halide is used as the first reactant; a second reactant containing oxygen and hydrogen atoms, for example, H 2 O and / or H 2 O 2 ; A ternary fatty amine catalyst is used to produce a silicon dioxide film on the functionalized surface of the substrate. In this embodiment of the present invention, the chemisorbed layer of the first reactant is along the substrate surface by exposing the functionalized surface of the substrate to a mixture of the first reactant and catalyst in a first process step. Form. The unreacted first reactant and by-products are then removed from that region of the substrate. In the next process step, the chemisorbed layer of the first reactant reacts with the second reactant in the presence of the ternary fatty compound amine catalyst. This by-product of the second process stage is removed from the substrate area.
本発明の実施形態について、反応触媒として第三脂肪族アミンの使用によって、プロセス効率、望まない副産物の除去又は最小化によって、及び、基板に堆積されたSiO2薄膜の純度及び品質において、新規でかつ全く不測の効果を奏する。さらに詳細には、一の窒素−水素(N−H)結合を有するアミン、例えば、アンモニア(NH3)、一元又は二元の脂肪族アミン(NR、H2、又はNR2H)を触媒として用いるならば、以下の式(1)及び(2)に示したように、シリコン−窒素(Si−N)結合を有する望まない副産物を形成する傾向があることがわかった:
(1)SiCl4+NR2H → Cl3Si−NR2+HCl
(2)SiCl4+NH3 → Cl3Si−NH4 +Cl−(塩)
ここで、Rは1個から5個程度の炭素原子を有する脂肪族群(CxHy)であり、脂肪族群Rは同じでも異なっていてもよい。
Embodiments of the present invention are novel in the use of tertiary aliphatic amines as reaction catalysts, in process efficiency, removal or minimization of unwanted by-products, and in the purity and quality of SiO 2 thin films deposited on substrates. And there is a totally unexpected effect. More specifically, an amine having one nitrogen-hydrogen (N—H) bond, such as ammonia (NH 3 ), one or two aliphatic amines (NR, H 2 , or NR 2 H) is used as a catalyst. If used, it has been found that there is a tendency to form unwanted by-products with silicon-nitrogen (Si-N) bonds, as shown in the following equations (1) and (2):
(1) SiCl 4 + NR 2 H → Cl 3 Si—NR 2 + HCl
(2) SiCl 4 + NH 3 → Cl 3 Si—NH 4 + Cl − (salt)
Here, R is an aliphatic group (C x H y ) having about 1 to 5 carbon atoms, and the aliphatic groups R may be the same or different.
しかしながら、(例えば、上述の式(1)及び(2)の右側に示したように)、表面層不純物につながる粒子の形成の主要な原因であり、堆積されたSiO2薄膜の品質を劣化することがわかった。対照的に、一般式NR3を有する第三脂肪族アミン(ここで、Rは1個から5個程度の炭素原子を有する脂肪族群(CxHy))が反応触媒として使用されるならば、シリコン−窒素(Si−N)結合を有する特別の副産物を実質的に形成しないことがわかっている。結果として、本発明の方法によって、より高品質でかつ優れた均一性を有するはるかに高純度のSiO2薄膜が堆積される。 However, it is a major cause of the formation of particles leading to surface layer impurities (eg, as shown on the right side of equations (1) and (2) above) and degrades the quality of the deposited SiO 2 thin film. I understood it. In contrast, if a tertiary aliphatic amine having the general formula NR3 (wherein R is an aliphatic group having about 1 to 5 carbon atoms (C x H y )) is used as the reaction catalyst, It has been found that it does not substantially form special by-products with silicon-nitrogen (Si-N) bonds. As a result, the method of the present invention deposits a much higher purity SiO 2 film with higher quality and better uniformity.
以下で議論する図7及び表3は、この知見の有効性と顕著な重要性を証明している。図7は、第三脂肪族アミンでないアミン触媒を用いてALDプロセスを実施するとき、固体の特別な副産物の形成を確認するRGA分析の結果である。図7は、第1の反応物としてSiCl4と、触媒してジメチルアミン((H3C)2NH)、すなわちN−H単結合を有するアミンとを用いるクラウス’442において教示された触媒型ALDプロセスに基づいている。残留質量スペクトル装置を、反応物からの副産物を分析するためにALD反応チャンバに結合した。図7の質量スペクトルでは、反応物の望まない(不必要な)副産物としてCl3Si−N(CH3)2の形成を確認した。このような副産物の形成は、SiCl4第1の反応物からSiのいくつかが、SiO2として基板表面に堆積する代わりに、副産物を形成する際に浪費されたことを意味する。 FIG. 7 and Table 3 discussed below demonstrate the validity and significant importance of this finding. FIG. 7 is the result of an RGA analysis confirming the formation of a solid byproduct when the ALD process is performed using an amine catalyst that is not a tertiary aliphatic amine. FIG. 7 shows the catalyst type taught in Claus' 442 using SiCl 4 as the first reactant and catalyzed by dimethylamine ((H 3 C) 2 NH), ie, an amine having an N—H single bond. Based on ALD process. A residual mass spectrometer was coupled to the ALD reaction chamber for analyzing by-products from the reactants. The mass spectrum in FIG. 7 confirmed the formation of Cl 3 Si—N (CH 3 ) 2 as an unwanted (unnecessary) byproduct of the reactant. Such by-product formation means that some of the Si from the SiCl 4 first reactant was wasted in forming the by-product instead of depositing on the substrate surface as SiO 2 .
従来技術に対する本発明の実施形態の利点の他の証拠を以下の表3に示した。
表3では、第1の反応物としてSiCl4を用い、触媒として異なるアミンを用いて触媒型ALDが実施されたときに同じ領域の基板表面に堆積された(少なくとも0.16μmのサイズを有する)望まない粒子の数を比較している。表3は、ALD触媒としてSiCl4すなわち3個のN−H結合を有する分子を用いて、ALDプロセスがSiO2薄膜の表面上に数万の副産物粒子を生ずる。SiO2薄膜上のこの非常に高いレベルの粒子のコンタミネーションは半導体装置のパフォーマンスに反対に影響を与え、非常に過酷な現代の半導体用途の多くに対して全く受け入れられないものである。 In Table 3, the desired (with a size of at least 0.16 μm) deposited on the substrate surface in the same region when catalytic ALD was performed using SiCl 4 as the first reactant and a different amine as the catalyst. Not comparing the number of particles. Table 3, using a molecule with SiCl 4 ie three N-H bond as ALD catalyst, ALD processes produce tens of thousands of products particles on the surface of the SiO 2 thin film. This very high level of particle contamination on the SiO 2 thin film adversely affects the performance of the semiconductor device and is totally unacceptable for many of the very demanding modern semiconductor applications.
表3は、ALD触媒としてジメチルアミン、すなわち単一の攻撃されやすいN−H結合の使用は、約1桁のオーダーで粒子状副産物を低減するのに有効であることを示している。ジメチルアミン触媒と共に得られるように、SiO2薄膜上に数1000の範囲で粒子製造でさえ、非常に高いパフォーマンスの半導体装置に対する許容範囲を越えている。表3は、ALD触媒としてトリメチルアミンを使用して、それによって攻撃されやすい全N−H結合を除去することによって、アンモニアに対して3桁のオーダーの減少であり、ジメチルアミンに対して2桁のオーダーである数10まで副産物粒子の生成を減少するという劇的でかつ不測の結果を示していることを明らかにしている。、 Table 3 shows that the use of dimethylamine, a single susceptible N—H bond, as an ALD catalyst is effective in reducing particulate byproducts on the order of about an order of magnitude. So as to obtain with dimethyl amine catalyst, even at particle production in the range number 1000 of the SiO 2 thin film is beyond the allowable range for the semiconductor device of very high performance. Table 3 shows a reduction of 3 orders of magnitude for ammonia and 2 orders of magnitude for dimethylamine by using trimethylamine as an ALD catalyst and removing all the NH bonds susceptible to attack by it. It reveals dramatic and unforeseen consequences of reducing by-product particle production to the order of several tens. ,
従来技術に対する本発明のこの実施形態の他の利点は、この本発明の実施形態が、例えば、クラウス’442特許において好適な触媒であるピリジンの代わりに第三脂肪族アミン触媒を使用することである。ピリジンは、C5H5Nの化学式を有して5個の炭素原子及び1個の窒素原子のリングを含む異種環状化合物である。これは室温で、刺激的で特徴的な臭いを有しかつ十分に取り扱いに注意を要する有毒液体として存在する。ALDプロセスにおいて触媒として用いられるときは、ピリジンは蒸発して気体状態(ピリジンの沸点は115.5℃)になる。従って、ピリジンを処理する装備は複雑であり、ピリジン供給ラインは容易に汚染される。 Another advantage of this embodiment of the present invention over the prior art is that this embodiment of the present invention uses a tertiary aliphatic amine catalyst instead of pyridine, which is a suitable catalyst in, for example, the Claus' 442 patent. is there. Pyridine is a heterocycle that has a chemical formula of C 5 H 5 N and contains a ring of 5 carbon atoms and 1 nitrogen atom. It exists at room temperature as a toxic liquid that has an irritating and characteristic odor and requires careful handling. When used as a catalyst in an ALD process, pyridine evaporates to a gaseous state (the boiling point of pyridine is 115.5 ° C.). Thus, the equipment for treating pyridine is complex and the pyridine supply line is easily contaminated.
対照的に、低分子量の第三脂肪族アミン例えば、トリメチルアミンは周囲条件で気体であり、それによって通常の反応条件で相変化を生じる傾向がある触媒より使用を容易になっている。さらに、トリメチルアミンの毒性はピリジンの毒性よりはるかに低く、トリメチルアミンの沸点は3〜4℃である。 In contrast, low molecular weight tertiary aliphatic amines such as trimethylamine are easier to use than catalysts which are gaseous at ambient conditions and thereby tend to undergo phase changes at normal reaction conditions. Furthermore, the toxicity of trimethylamine is much lower than that of pyridine, and the boiling point of trimethylamine is 3-4 ° C.
第3の実施形態
本発明の第3の好適な実施形態では、本発明の先述の2つの実施形態の利点と効果の全ては実現できない場合は多い。この実施形態では、第1の反応物として少なくとも2個又は3個以上のシリコン原子を有するシリコン化合物すなわちSi2Cl6のようなシリコンハライドと、第2の反応物としてO原子及びH原子を含む化合物例えば、H2O及び/又はH2O2と、第三脂肪族アミン触媒とを用いて、基板の機能化表面上に二酸化シリコン薄膜を成長させる。
Third Embodiment In the third preferred embodiment of the present invention, it is often impossible to realize all of the advantages and effects of the two previous embodiments of the present invention. In this embodiment, the first reactant comprises a silicon compound having at least two or more silicon atoms, ie a silicon halide such as Si 2 Cl 6 , and the second reactant comprises O and H atoms. A silicon dioxide thin film is grown on the functionalized surface of the substrate using compounds such as H 2 O and / or H 2 O 2 and a tertiary aliphatic amine catalyst.
この本発明の実施形態では、基板表面に沿って第1の反応物の化学吸着層を形成するために、第1のプロセス段階において、第1の反応物と第三脂肪族アミン触媒の混合物に、基板の機能化表面を曝す。反応しなかった第1の反応物と副産物とを基板の領域から除去する。次のプロセス段階では、第1の反応物の化学吸着層は、第三脂肪族アミン触媒の存在下で第2の反応物と反応する。この第2の反応段階の副産物を基板領域から除去する。 In this embodiment of the present invention, the first reactant and the tertiary aliphatic amine catalyst are mixed in a first process stage to form a chemisorbed layer of the first reactant along the substrate surface. Expose the functionalized surface of the substrate. The unreacted first reactant and by-products are removed from the area of the substrate. In the next process step, the first reactant chemisorbed layer reacts with the second reactant in the presence of a tertiary aliphatic amine catalyst. This by-product of the second reaction stage is removed from the substrate region.
本発明の他の実施形態では、図1の複数のプロセス段階132−138のうちの一又は二以上に対して気体パルス/パージ法の使用によって、本発明の方法の効率を改善し、プロセスコンタミネーションを除去し、基板上に形成されたSiO2薄膜の質を改善することができることがわかった。図8は、以下に記載するように、図1の段階132−138を実施する気体パルス法を図示するものである。 In another embodiment of the present invention, the use of a gas pulse / purge method for one or more of the plurality of process stages 132-138 of FIG. 1 improves the efficiency of the method of the present invention and improves process contamination. It was found that the nation can be removed and the quality of the SiO 2 thin film formed on the substrate can be improved. FIG. 8 illustrates a gas pulse method for performing steps 132-138 of FIG. 1 as described below.
段階132
第1の反応物と適当な触媒とを独立の各供給ラインを介して反応チャンバに流す。このとき、第1の反応物と触媒の混合ガスからのコンタミネーションを回避するために、第2の反応供給ラインを介して不活性ガス例えば、アルゴンガスをチャンバに流すことができる。
The first reactant and a suitable catalyst are flowed to the reaction chamber via each independent supply line. At this time, in order to avoid contamination from the mixed gas of the first reactant and the catalyst, an inert gas such as argon gas can be flowed into the chamber through the second reaction supply line.
段階134
パージのための不活性ガスを、第1の反応物供給ラインと第2の反応物供給ラインと触媒供給ラインとを介してチャンバに流し込む。
An inert gas for purging is flowed into the chamber through the first reactant supply line, the second reactant supply line, and the catalyst supply line.
段階136
O原子とH原子とを含む第2の反応物と適当な触媒とを、独立の各供給ラインを介してチャンバに流し込む。このとき、第1の反応物供給ラインをパージするため、第1の反応物供給ラインを介して、不活性ガス例えば、アルゴンガスをチャンバ内に流し込むことができる。
A second reactant containing O and H atoms and a suitable catalyst are flowed into the chamber via each independent supply line. At this time, in order to purge the first reactant supply line, an inert gas such as argon gas can be flowed into the chamber via the first reactant supply line.
段階138
パージのための不活性ガスを、第1の反応物供給ラインと第2の反応物供給ラインと触媒供給ラインとを介してチャンバに流し込む。
An inert gas for purging is flowed into the chamber through the first reactant supply line, the second reactant supply line, and the catalyst supply line.
10秒間のプロセス時間間隔(インターバル)にわたって、図1の段階132−138に対応して、種々のフィードラインと反応物チャンバに気体のパルス送り/排気又はパージについての複数の代表的な“レシピ”又はシーケンスを、図9−図12に示す。図9は、副産物をパージし除去するために不活性ガスを用いて選択したプロセス時間間隔で行われる1サイクルに以下の段階を備えたプロセスパージシーケンスを示している:0−2秒プロセス時間−HCD供給;2−4秒プロセス時間−パージ;4−7.5秒プロセス時間−H2O供給;7.5−10秒プロセス時間−パージ。図10は、1サイクルにおいて連続する以下の段階を備えた、排気圧力が第1及び第2の反応物供給圧力より低いプロセス排気シーケンスを示す:0−2秒プロセス時間−HCD供給;2−4秒プロセス時間−排気;4−7.5秒プロセス時間−H2O供給;7.5−10秒プロセス時間−排気。図11は、1サイクルにおいて連続する以下の段階を備えた、排気がパージ後に用いられるプロセスパージ−排気シーケンスを示す:0−2秒プロセス時間−HCD供給;2−3秒プロセス時間−パージ;3−4秒プロセス時間−排気;4−7.5秒プロセス時間−H2O供給;7.5−8.5秒プロセス時間−パージ:8.5−10秒プロセス時間−排気。図12は、1サイクルにおいて連続する以下の段階を備えた、パージが排気後に用いられるプロセス排気−パージシーケンスを示す:0−2秒プロセス時間−HCD供給;2−3秒プロセス時間−排気;3−4秒プロセス時間−パージ;4−7.5秒プロセス時間−排気;7.5−8.5秒プロセス時間−排気:8.5−10秒プロセス時間−パージ。 A plurality of exemplary “recipes” for pulsing / evacuating or purging gas to various feed lines and reactant chambers over a 10 second process time interval, corresponding to steps 132-138 of FIG. Alternatively, the sequence is shown in FIGS. FIG. 9 shows a process purge sequence with the following steps in one cycle performed at selected process time intervals using an inert gas to purge and remove by-products: 0-2 second process time— HCD supply; 2-4 seconds process time - purge; 4-7.5 seconds process time -H 2 O supply; 7.5-10 seconds process time - purge. FIG. 10 shows a process exhaust sequence in which the exhaust pressure is lower than the first and second reactant supply pressures with the following steps consecutive in one cycle: 0-2 seconds process time—HCD supply; 2-4 seconds process time - exhaust; 4-7.5 seconds process time -H 2 O supply; 7.5-10 seconds process time - the exhaust. FIG. 11 shows a process purge-evacuation sequence in which exhaust is used after purging, with the following steps consecutive in one cycle: 0-2 second process time-HCD supply; 2-3 second process time-purge; -4 sec process time - exhaust; 4-7.5 seconds process time -H 2 O supply; 7.5-8.5 seconds process time - purge: 8.5-10 seconds process time - the exhaust. FIG. 12 shows a process evacuation-purge sequence in which purge is used after evacuation, with the following steps consecutive in one cycle: 0-2 second process time-HCD supply; 2-3 seconds process time-evacuation; 3 -4-second process time-purge; 4-7.5 second process time-exhaust; 7.5-8.5 second process time-exhaust: 8.5-10 second process time-purge.
本発明の他の実施形態では、本発明によって基板上にSiO2薄膜を成長させるために触媒補助型ALDを実施する温度条件は、2つの競合するプロセスパラメータを調和させることによって最適化する。図13に図示したように、一方で、触媒補助型ALDと第1の反応物として複数のシリコン原子を有する化合物(例えば、Si2Cl6)を用いてSiO2を形成する際の堆積速度は、温度に反比例する。図13は、一般に、プロセス温度が高いほど、堆積速度が低いことを示している。これは堆積速度に起因すると思われ、ALDが表面反応なので、それはALDプロセスの特有の特徴である。プロセス温度が高いほど、反応に参加する原子の表面脱離活性エネルギーは高い。結果として、表面での“滞在時間”は、以下の式に従って、反応が生ずるのに要する最小時間より短縮される:
A:アレニウス定数
Ed:脱離活性エネルギー
R:気体定数
T:温度
In another embodiment of the present invention, the temperature condition for carrying out the catalytic assisted ALD to grow an SiO 2 thin film on a substrate by the present invention is optimized by harmonizing the process parameters of two competing. On the other hand, as illustrated in FIG. 13, the deposition rate when forming SiO 2 using a catalyst-assisted ALD and a compound having a plurality of silicon atoms (for example, Si 2 Cl 6 ) as the first reactant is Inversely proportional to temperature. FIG. 13 generally shows that the higher the process temperature, the lower the deposition rate. This appears to be due to the deposition rate, and since ALD is a surface reaction, it is a unique feature of the ALD process. The higher the process temperature, the higher the surface desorption activity energy of the atoms participating in the reaction. As a result, the “residence time” at the surface is reduced from the minimum time required for the reaction to take place according to the following equation:
プロセス温度が高いほど、基板表面でのO−H鎖の脱ヒドロキシル化(脱水酸化)が容易になる。従って、表面に沿った反応サイトの数は減少し、堆積速度は小さくなる。 The higher the process temperature, the easier the dehydroxylation (dehydration oxidation) of the O—H chain on the substrate surface. Thus, the number of reaction sites along the surface is reduced and the deposition rate is reduced.
他方、図14に図示したように、3個の異なるプロセス温度での炭素含有量の経時変化のSIMS(二次イオンマススペクトロメータ)グラフでは、ALD堆積SiO2薄膜の炭素含有量もプロセス温度によって変化する。通常、低温プロセス温度では、ALD反応過程の炭素含有副産物は、プロセス中に基板表面から十分には除去されなく、堆積するSiO2薄膜に捕捉される。それによる薄膜の不純物レベルの増大によって、半導体装置の質は低下する。 On the other hand, as shown in FIG. 14, in the SIMS (secondary ion mass spectrometer) graph of the change over time of the carbon content at three different process temperatures, the carbon content of the ALD deposited SiO 2 thin film also depends on the process temperature. Change. Typically, at low process temperatures, carbon-containing byproducts of the ALD reaction process are not fully removed from the substrate surface during the process and are trapped in the deposited SiO 2 film. The resulting increase in the impurity level of the thin film degrades the quality of the semiconductor device.
従って、これらの2つのプロセスパラメータは、プロセス温度条件を最適化するために互いに釣り合わなければならない。先述の考察に基づいて、本発明のこの実施形態において、最適プロセス温度範囲は約90℃−110℃であることがわかった。 Therefore, these two process parameters must be balanced with each other to optimize process temperature conditions. Based on the foregoing considerations, it has been found that in this embodiment of the invention, the optimum process temperature range is about 90 ° C-110 ° C.
本発明の他の実施形態では、本発明に従って基板上にSiO2薄膜を成長させるために触媒補助型ALDを実施する圧力条件は、2つの競合するプロセスパラメータを調和させることによって最適化する。図15に図示したように、一方で、触媒補助型ALDを用いてSiO2を形成する際の堆積速度は、圧力に反比例する。すなわち、圧力が高いほど、所定の時間間隔/ALDサイクル数にわたって堆積されたSiO2膜は厚い。 In another embodiment of the present invention, the pressure conditions for performing catalyst assisted ALD to grow a SiO 2 thin film on a substrate according to the present invention are optimized by matching two competing process parameters. On the other hand, as illustrated in FIG. 15, the deposition rate when forming SiO 2 using catalyst-assisted ALD is inversely proportional to the pressure. That is, the higher the pressure, the thicker the SiO 2 film deposited over a predetermined time interval / ALD cycle number.
他方、図16は、SiO2薄膜のプロセス圧力と非均一度(性)との間に非線形関係が存在することを示している。従って、図16は、ある点まで、より高いプロセス圧力が堆積された層の非均一度を低減する;しかし、この点を越えると、より高い圧力はより高い非均一度と相関する。 On the other hand, FIG. 16 shows that a non-linear relationship exists between the process pressure and the non-uniformity (sex) of the SiO 2 thin film. Thus, FIG. 16 up to a point reduces the non-uniformity of the deposited layer with higher process pressure; however, beyond this point, higher pressure correlates with higher non-uniformity.
従って、これらのプロセスパラメータは、プロセス圧力条件を最適化するために、互いに釣り合わなければならない。以上の考察をもとに、本発明の実施形態に対応して、最適プロセス圧力範囲が約50mmTorr〜約5Torrの範囲であると決定された。 Therefore, these process parameters must be balanced with each other in order to optimize process pressure conditions. Based on the above considerations, the optimum process pressure range was determined to be in the range of about 50 mm Torr to about 5 Torr in accordance with embodiments of the present invention.
ここに記載された本発明の範囲を逸脱することなく、高パフォーマンス半導体装置における使用のために、基板表面上でのSiO2薄膜の上述の改良型触媒補助ALD形成について、さらに他の変更及び変形が可能であることは当業者には明らかであり、上述の詳細な説明に含まれる全事項は例示に過ぎず、限定的な意味に解釈されてはならないことは理解されたい。 Without departing from the scope of the invention described herein, for use in high-performance semiconductor device, the above-mentioned improved catalysts assist ALD formation of the SiO 2 thin film on the substrate surface, yet other modifications and variations It will be apparent to those skilled in the art that all matters contained in the above detailed description are illustrative only and should not be construed in a limiting sense.
Claims (33)
以下の段階(a)から段階(b)、すなわち、;
(a)少なくとも2つのシリコン原子を有するシリコン化合物から成る群から選択された少なくとも一の要素を含む第1の反応物と、アンモニアとアミンとから成る群から選択された第1の触媒とを用いる段階;
(b)少なくとも2つのシリコン原子を有するシリコン化合物から成る群から選択された少なくとも一の要素を含む第1の反応物を用いることと、第三脂肪族アミン化合物から成る群から選択された少なくとも一の要素を含む第1の触媒を用いることと、を組み合わせて用いる段階;
のうちの少なくとも一を備え、
前記第2の反応物がH 2 OとオゾンとH 2 O 2 とから成る群から選択されたものであり、
前記第2の触媒がアンモニアとアミンとから成る群から選択されたものであり、
前記方法が、各反応段階に続いて、反応しなかった反応物と触媒と反応物副産物とを基板表面から除去する段階を備えた方法。 A method of forming a silicon dioxide layer on a substrate surface of a semiconductor product using a catalyst assisted atomic layer deposition process, wherein the functionalized surface of the substrate is a first mixture comprising a first reactant and a first catalyst. And then exposing the surface to a second mixture of a second reactant and a second catalyst to form a silicon dioxide monolayer on the substrate surface. In the method
From step (a) to step ( b ):
(A) using a first reactant comprising at least one element selected from the group consisting of silicon compounds having at least two silicon atoms, and a first catalyst selected from the group consisting of ammonia and amines. Stage;
(B) and the use of the first reactant comprising at least one member selected from the group consisting of silicon compounds having two silicon atoms even without low, selected from the group consisting of tertiary aliphatic amine compound Using a first catalyst comprising at least one element in combination;
Comprising at least one of
The second reactant is selected from the group consisting of H 2 O, ozone and H 2 O 2 ;
The second catalyst is selected from the group consisting of ammonia and an amine;
The method comprises the steps of removing unreacted reactants, catalyst and reactant by-products from the substrate surface following each reaction step.
(a)N2、O2、H2、及びArから成る群から選択された不活性ガスの存在下で、300℃−900℃で二酸化シリコン層をアニールすることを備えた熱処理;
(b)O2又はH2の存在下で、200℃−700℃で二酸化シリコン層をアニールすることを備えたプラズマ処理;
(c)25℃−700℃で、二酸化シリコン層をO3に曝すことを備えたオゾン処理;
のうちの一つから選択されたものである請求項14に記載の方法。 Said curing step is the following:
(A) in the presence of N 2, O 2, H 2 , and an inert gas selected from the group consisting of Ar, heat treatment with the annealing the silicon dioxide layer at 3 00 ℃ -900 ℃;
(B) plasma treatment comprising annealing the silicon dioxide layer at 200 ° C.-700 ° C. in the presence of O 2 or H 2 ;
(C ) ozone treatment comprising exposing the silicon dioxide layer to O 3 at 25 ° C.-700 ° C .;
The method of claim 1 4 are those selected from one of the.
プロセス時間長t1の間、前記基板を含む領域に前記第1の反応物と第1の触媒とを供給する段階:時間長t1の直後に、時間長t2の間、領域を不活性ガスでパージする段階:時間長t2の直後に、時間長t3の間、領域から不活性ガスと他の気体物質を少なくとも部分的に排出するために領域を排気する段階:時間長t3の直後に、時間長t4の間、前記第2の反応物と第2の触媒とを領域へ供給する段階:時間長t4の直後に、時間長t5の間、領域を不活性ガスでパージする段階:時間長t5の直後に、時間長t6の間、領域から不活性ガスと他の気体物質とを少なくとも部分的に排出するために領域を排気する段階:というシーケンスに従って各原子層堆積のためにパージ−排気処理を備えた請求項1に記載の方法。 The following sequence:
Supplying the first reactant and the first catalyst to the region including the substrate for a process time length t 1 : immediately after the time length t 1 , the region is inactivated for a time length t 2 step purging with gas: immediately after the time length t 2, during the duration t 3, step to evacuate the area in order to at least partially discharge the inert gas and other gaseous materials from the region: the time length t 3 immediately after, during the time length t 4, the second reactant and a second catalyst comprising: a supply to the region of: immediately after the time length t 4, during the time length t 5, the region inert gas Purging with: each step according to a sequence of: immediately following time length t 5 , evacuating the region to discharge at least partially inert gas and other gaseous substances from the region for a time length t 6 : The method of claim 1 comprising a purge-evacuation process for atomic layer deposition.
プロセス時間長t1の間、前記基板を含む領域に前記第1の反応物と第1の触媒とを供給する段階:時間長t1の直後に、時間長t2の間、領域から少なくとも部分的に気体物質を排出するために領域を排気する段階:時間長t2の直後に、時間長t3の間、領域を不活性ガスでパージする段階:時間長t3の直後に、時間長t4の間、前記第2の反応物と第2の触媒とを領域へ供給する段階:時間長t4の直後に、時間長t5の間、領域から気体物質を少なくとも部分的に排出するために領域を排気する段階:時間長t5の直後に、時間長t6の間、領域を不活性ガスでパージする段階:というシーケンスに従って各原子層堆積のためにパージ−排気処理を備えた請求項1に記載の方法。 The following sequence:
Supplying the first reactant and the first catalyst to the region including the substrate for a process time length t 1 : immediately after the time length t 1 and at least partly from the region for a time length t 2 stages to evacuate the area in order to discharge the gaseous substance: immediately after the time length t 2, during the duration t 3, step purging region with inert gas: immediately after the duration t 3, the time length between t 4, the second reactant and a second catalyst comprising: a supplied to the region: immediately after the length of time t 4, during the time length t 5, at least partially discharging the gaseous material from the area For each atomic layer deposition, a purge-evacuation process was provided according to the sequence: evacuating the region for: immediately following time length t 5 and purging the region with inert gas for time length t 6 The method of claim 1.
(b)第1の反応物と触媒と任意で不活性ガスとをチャンバに供給する段階であって、前記第1の反応物は少なくとも2個のシリコン原子を有するシリコンハライド化合物であり、前記触媒はアンモニアとアミンから成る群から選択されたものである段階と;
(c)反応副産物と反応しなかった第1の反応物と触媒とをチャンバからパージする段階と;
(d)第2の反応物と触媒と任意で不活性ガスとをチャンバに供給する段階であって、前記第2の反応物は酸素成分を有する化合物であり、前記触媒はアンモニアとアミンとから成る群から選択されたものである段階と;
(e)反応副産物と反応しなかった第2の反応物と触媒とをチャンバからパージする段階と;
(f)二酸化シリコン薄膜が所望の膜厚になるまで段階(a)−(e)を繰り返す段階と;
を備えた基板表面に二酸化シリコン薄膜を形成する方法。 (A) introducing a substrate into the chamber;
(B) supplying a first reactant, a catalyst and optionally an inert gas to the chamber, wherein the first reactant is a silicon halide compound having at least two silicon atoms; Is a stage selected from the group consisting of ammonia and amines;
(C) purging from the chamber the first reactant and catalyst that have not reacted with the reaction by-products;
(D) supplying a second reactant, catalyst, and optionally an inert gas, to the chamber, wherein the second reactant is a compound having an oxygen component, the catalyst comprising ammonia and an amine. A stage selected from the group consisting of;
(E) purging from the chamber the second reactant and catalyst that have not reacted with the reaction byproduct;
(F) repeating steps (a)-(e) until the silicon dioxide thin film has the desired thickness;
A method of forming a silicon dioxide thin film on a substrate surface comprising:
プロセス時間長t1の間、前記チャンバに前記第1の反応物と触媒とを供給する段階;時間長t1の直後に、時間長t2の間、チャンバを不活性ガスでパージする段階;時間長t2の直後に、時間長t3の間、チャンバから不活性ガスと他の気体物質を少なくとも部分的に排出するために領域を排気する段階;時間長t3の直後に、時間長t4の間、前記第2の反応物と触媒とをチャンバへ供給する段階:時間長t4の直後に、時間長t5の間、チャンバを不活性ガスでパージする段階:時間長t5の直後に、時間長t6の間、チャンバから不活性ガスと他の気体物質とを少なくとも部分的に排出するために領域を排気する段階:というシーケンスに従って実施する請求項18に記載の方法。 Steps (b) to (e) are performed in the following sequence:
Supplying the first reactant and catalyst to the chamber for a process time length t 1 ; purging the chamber with an inert gas for a time length t 2 immediately after the time length t 1 ; immediately after the time length t 2, during the duration t 3, step to evacuate the area in order to at least partially discharge the inert gas and other gaseous material from the chamber; immediately after the duration t 3, the time length between t 4, the second reactant and the catalyst comprising: a supplying to the chamber: immediately after the time length t 4, during the time length t 5, step purging the chamber with an inert gas: time length t 5 the method of claim 1 8 carried out according to a sequence that: immediately after, during the time length t 6, the step of evacuating the space to at least partially discharge the inert gas and other gaseous material from the chamber of .
プロセス時間長t1の間、前記チャンバに前記第1の反応物と触媒とを供給する段階;時間長t1の直後に、時間長t2の間、チャンバから少なくとも部分的に気体物質を排出するためにチャンバを排気する段階;時間長t2の直後に、時間長t3の間、チャンバを不活性ガスでパージする段階;時間長t3の直後に、時間長t4の間、前記第2の反応物と触媒とをチャンバへ供給する段階;時間長t4の直後に、時間長t5の間、チャンバから気体物質を少なくとも部分的に排出するためにチャンバを排気する段階;時間長t5の直後に、時間長t6の間、チャンバを不活性ガスでパージする段階:というシーケンスに従って実施する請求項18に記載の方法。 Steps (b) to (e) are performed in the following sequence:
Supplying the first reactant and catalyst to the chamber for a process time length t 1 ; immediately after the time length t 1 , at least partially exhausting gaseous material from the chamber for a time length t 2 Evacuating the chamber to perform; purging the chamber with inert gas immediately after time length t 2 for a time length t 3 ; immediately after time length t 3 , for a time length t 4 Supplying a second reactant and catalyst to the chamber; immediately after time length t 4 , evacuating the chamber to at least partially exhaust gaseous material from the chamber for a time length t 5 ; time The method of claim 18 , wherein the method is performed according to a sequence immediately after length t 5 , purging the chamber with inert gas for a time length t 6 .
(b)第1の反応物と触媒と任意で不活性ガスとをチャンバに供給する段階であって、前記第1の反応物は少なくとも2つのシリコン原子を有するシリコン化合物から成る群から選択された少なくとも一の要素を含み、前記触媒は第三脂肪族アミンである段階と;
(c)チャンバから反応副産物と反応しなかった第1の反応物と触媒をパージする段階と;
(d)第2の反応物と触媒と任意で不活性ガスとをチャンバに供給する段階であって、前記第2の反応物は酸素成分を有する化合物であり、前記触媒はアンモニアとアミンとから成る群から選択されたものである段階と;
(e)チャンバから反応副産物と反応しなかった第2の反応物と触媒をパージする段階と;
(f)二酸化シリコン薄膜が所望の膜厚になるまで段階(a)−(e)を繰り返す段階と;
を備えた基板表面に二酸化シリコン薄膜を形成する方法。 (A) introducing a substrate into the chamber;
(B) supplying a first reactant, catalyst and optionally an inert gas to the chamber, wherein the first reactant is selected from the group consisting of silicon compounds having at least two silicon atoms; Comprising at least one element , wherein the catalyst is a tertiary aliphatic amine;
(C) purging the first reactant and catalyst that have not reacted with the reaction by-products from the chamber;
(D) supplying a second reactant, catalyst, and optionally an inert gas, to the chamber, wherein the second reactant is a compound having an oxygen component, the catalyst comprising ammonia and an amine. A stage selected from the group consisting of;
(E) purging the chamber with a second reactant that has not reacted with reaction byproducts and the catalyst;
(F) repeating steps (a)-(e) until the silicon dioxide thin film has the desired thickness;
A method for forming a silicon dioxide thin film on a substrate surface comprising:
プロセス時間長t1の間、前記チャンバに前記第1の反応物と触媒とを供給する段階;時間長t1の直後に、時間長t2の間、チャンバを不活性ガスでパージする段階;時間長t2の直後に、時間長t3の間、チャンバから不活性ガスと他の気体物質とを少なくとも部分的に排出するために領域を排気する段階;時間長t3の直後に、時間長t4の間、前記第2の反応物と触媒とをチャンバへ供給する段階:時間長t4の直後に、時間長t5の間、チャンバを不活性ガスでパージする段階:時間長t5の直後に、時間長t6の間、チャンバから不活性ガスと他の気体物質とを少なくとも部分的に排出するために領域を排気する段階:というシーケンスに従って実施することを備えた請求項27に記載の方法。 Steps (b) to (e) are performed in the following sequence:
Supplying the first reactant and catalyst to the chamber for a process time length t 1 ; purging the chamber with an inert gas for a time length t 2 immediately after the time length t 1 ; immediately after the time length t 2, during the duration t 3, step to evacuate the area in order to at least partially discharge the inert gas and other gaseous material from the chamber; immediately after the duration t 3, time during the long t 4, the second reactant and the catalyst comprising: a supplying to the chamber: immediately after the time length t 4, during the time length t 5, step purging the chamber with an inert gas: the time length t 3. Immediately following 5, the operation is performed according to a sequence of: evacuating the region to at least partially evacuate the inert gas and other gaseous substances from the chamber for a time length t 6. 8. The method according to 7 .
プロセス時間長t1の間、前記チャンバに前記第1の反応物と触媒とを供給する段階;時間長t1の直後に、時間長t2の間、チャンバから少なくとも部分的に気体物質を排出するためにチャンバを排気する段階;時間長t2の直後に、時間長t3の間、チャンバを不活性ガスでパージする段階;時間長t3の直後に、時間長t4の間、前記第2の反応物と触媒とをチャンバへ供給する段階;時間長t4の直後に、時間長t5の間、チャンバから気体物質を少なくとも部分的に排出するためにチャンバを排気する段階;時間長t5の直後に、時間長t6の間、チャンバを不活性ガスでパージする段階:というシーケンスに従って実施することを備えた請求項27に記載の方法。 Steps (b) to (e) are performed in the following sequence:
Supplying the first reactant and catalyst to the chamber for a process time length t 1 ; immediately after the time length t 1 , at least partially exhausting gaseous material from the chamber for a time length t 2 Evacuating the chamber to perform; purging the chamber with inert gas immediately after time length t 2 for a time length t 3 ; immediately after time length t 3 , for a time length t 4 Supplying a second reactant and catalyst to the chamber; immediately after time length t 4 , evacuating the chamber to at least partially exhaust gaseous material from the chamber for a time length t 5 ; time immediately after the length t 5, during the duration t 6, the step of purging the chamber with an inert gas: the method according to claim 2 7 having to be carried out according to the sequence of.
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- 2003-06-12 US US10/459,943 patent/US6992019B2/en not_active Expired - Lifetime
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- 2003-06-24 EP EP03253968A patent/EP1383163B1/en not_active Expired - Lifetime
- 2003-06-30 CN CNB031330193A patent/CN100343960C/en not_active Expired - Lifetime
- 2003-07-07 JP JP2003271607A patent/JP4422445B2/en not_active Expired - Fee Related
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TW200407981A (en) | 2004-05-16 |
TWI237311B (en) | 2005-08-01 |
EP1383163B1 (en) | 2012-03-28 |
KR20040005568A (en) | 2004-01-16 |
EP1383163A3 (en) | 2004-07-07 |
CN100343960C (en) | 2007-10-17 |
EP1383163A2 (en) | 2004-01-21 |
US6992019B2 (en) | 2006-01-31 |
CN1480998A (en) | 2004-03-10 |
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